New azo dyestuffs



Patented Aug. 16, 1932 UNITED STATES KUSEN-ON-THE- RI-IINE, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC

WINFRID HENTRICH, 0F WIESDORF -ON-lI-IE-RI-IINE, LAND RUDOLF KNOCHEQOF LEVER- OF NEW YORK, N. Y., A CORPORATION OF DELAWARE NEW Azo nvns'rurrs No Drawing. Application filed February 29, 1928, Serial No. 258,142, and in, Germany March '12, 1927;

.The present invention relates to new azo dyestuffs of the general formula: p Ry-o-(cmn-co-NRaN=N R3 wherein R stands foran aromatic nucleus of the benzene or "naphthalene series, which may be substituted bylhalogen, a nitro or alkyl-group, R stands for hydrogen which may be replaced by alkyl, one R stands for the residue of a coupling component capable of producing an fazodyestuii, andthe other R stands for the residue of a diazotization component capable of producing an azodyestuflf which may contain a further N=N bers one, two and three. 7

According to our invention the new dyestuffs may be prepared by causing a compound of the general formula:

ni-ownnx-cdy wherein R and 03 have the above indicated meaning and 3 stands for a halogen atom, to

aryl resldue and 0: stands for one of the numreact upon a compound of the general forwherein R and m have the above inclicated meaning or by causing any diazocompound containing the same group R O- (OH )g-CO linked to a nitrogen atom to react upon any coupling component. Our new dyestufls are various colored powders, soluble in water if they contain a sultonic acid or carboxylic acid group. In an acid bath they dye wool evenly various shades of good fastness to light and fulling. They are also suitable for discharge printing on wool and for the production of valuable lakes or pigments.

The following examples will illustrate our invention without limiting it theretoz Example 1.'.-'93 partsby weightof aniline are diazotized andcoupled with 497 parts by weight of the sodium salt of the l-phenoxy acetylamino -8- hydroxynaphthalene 3.6-disulfonic acid in solution'rendered alka line-with sodium carbonate.

can be used as desired, for example 2-aminof benzoic acid, 2acet-amino-5-aminoanisol,' {laminoacetanilide or p'ara-xylidine, when different shades are obtained, while the dyestuiis possess similar properties Likewise the phenoxyacetyl residue canbe replaced by similar residues, for example, by the 2- (or 4-)-chloro;phenoxyacetyl-, the 3-(or id-I litrophenoxy acetyh, the 2.-chloro-4c-methylphenoxy-B-propionyl: I

or the 1-i(or 2-)l-naphthoxyacetyl ,residue. Furthermore the l-amino-8-hydroxynaph-r thalene-3.6-disultonic acid can be replaced by other aminoaphtholsulionic acids, such for example as, the 1-ethylamino-8 hydr0xynaphthalene-3.6-disulfonic acid and the like. 7 The .dyestuff aniline-azo-l- (U-chlorophenoxyacetyl-amino 8 hydroxynaphthalene ib-disultonic acid dyes wool apowerful-yellowish redshade. V

' When a slight excess above one mol. of

phenoxyacetylchloride is caused to act ,at

about 30-40 C. in the presence ofan agent combining with acid on themonoazo dyestuti' derived from one mol. of diazobenzene and one mol. 7 of l-amino-.8-hydroxynaphtha1ene- 3.6-disulfonic acid (coupled in alkaline solution), the same dyestufi is obtained as described at the beginning of this example.

Example 2.750 parts by weight of the sodium salt of the monoazo dyestuff, obtainable by coupling in'acid solution the diazo compound of one mol. of the 4-nitro-l-amino benzene-2-sulfonic acid with one mol. of the 2- (w-aminoethyl-amino) -naphthalene -7 sulionic acid, are dissolved in 50 litresof water and 600 parts by weight of 2-chloro-phenoxyacetyl chloride are added slowly drop by drop at about 3840 0., while stirring well. In

' order to complete the reactionthe mixture is heated for a short timeto 0., the new p oduct is salted out with a little common salt, pressed and dried. a

Obviously the 2 (w-2-chlorophenoxyacetylamino ethylamino) naphtl1alene-7-sulfonicacid of the formula:

may be produced first and then coupled with the diazo compound of 4snitro-l-aminoben zene-2-sulfonic acid. The resulting dyestufl is identical with that of the preceding process. It dyes wool evenly a very clear reddish violet. The dyeing is particularly fast to light,

fulling and perspiration.

' "As in Example 1 the diazo components,

the coupling components and also the aryl- 'oxyacyl residues-may be varied very widely. Thus, for example, the dyestufi obtainable from the diazo compound of 4.6-dinitro-1- aminobenzene-2-sulfonic acid by coupling with the 2- (w-4-1nethylphenoxyacetylaminoethylamino-) -naphthalene-6-sulfonic a c i d "4770 gives on wool a pure reddish blue, possessin the fastness properties described above. quite similar dyestufi is'produced from the diazo'compound of the 4.6-dinitro-1-aminoand water.

Other substituted aminoor aminoazo-compounds of the benzene or naphthalene series can be used as diazo components as desired. For example, the dyestufi obtainable from the diazo compound of the 4-chloro-2-anisidine and the 1-(4'-chlorophenoxyacetylamino) -8- hydroxynaphthalene-4.6-disulfonic acid is a bluish red.

Example 4-242 parts by weight of 4- amino-l-phenoxy-acetylamiho benzene are dissolved in hot water and filtered while stirring on to ice. The solution is acidified with hydrochloric acid, diazotized and coupled with 254 parts by weight of 1-(4-sul:Eo-)- phenyl-3-methyl-5-pyrazolone in solution rendered alkaline with sodium carbonate. The dyestuii is isolated by working up the reaction mixture in the customary manner and is obtained in a very good yield; it dyes wool evenly clear, golden yellow shadesof remarkable fastness to light and fulling.

The phenoxyacetyl residue in the 1.4 phenylene-diamine can be replaced by simi lar residues, for example, by the 2-(or 4-) chlorophenoxyacetyl-, the 2-(or 4-) -nitro phenoxyacetyl-, the B- (2-methylphenoxy-) propionyl, or the 1- (or 2-)-napthoxyacetyl residues. Likewise homologuesor substitution products of the phenoxy-acetylated 1.4-phenylene-diamine can be used as diazo components, for example 2-amino-4-phenoxyacetylamino-l-methoxybenzene or 4-amino-2-N-methyl-N-phenoxyacetylamino-l-methylbenzene odors-0O or also 4-amino-1-N-ethyl-N-phenoxyacetylaminobenzene,

- o o OHr-O-O the diazo compounds of which, for example, by coupling in alkaline solution with 2- methylamino 8 hydroxynaphthalene 6 -sul fonic acid yields a very even, brown, fast to fulling and light.

Other pyrazolon'es, methylketol and its sulfoniclacid can be used as coupling components, as Well as any desired aminonaphthol sulfonic acids and the N-alkyl or acidyl substitution products thereof. v

The dyestufl' described in this example is likewise obtainable by introducing the phenoxy acetyl residue after the production of CHry-O the dyestuff. This can be eflected in about U the following manner:

372 parts by weight of the aminoazo compound obtainable for example by the partial reduction of the monoazo dyestufl' from a-nitraniline and 1- (4'-sulfo) -phenyl-3- methyl-5-pyrazolone are treated with 250 parts by weight of phenoxyacetyl chloride in aqueous solution at 40 C. with thorough stirring, the reaction mixture being maintained weakly alkaline by careful dropping in of a 10% sodium carbonate solution. ,The reaction is complete, when a test portion no longer reacts with nitrous acid. The product is salted out and worked up in the customary manner.

Eazample 5-242 parts by weight of 4- amino-1-phenoxyacetylaminobenzene are diazotized as in Example 4E andcoupledwith 304 7 Boss parts by weight of 1-napthol-3.G-disulfonic acid in a solution rendered alkaline by means of sodium carbonate. The dyestulf is isolated by working up the reaction mixture in the customary manner; it gives on wool clear, yellowish red even shades of very satisfactory fastness tofulling and light.

An orange of similar properties is obtained from the diazo compound of the 2- (N- phenoxyacetylamino N-ethyil)1-1-aminoben.-

by coupling with 2-naphthol-6.8-disulfonic acid.

Valuable monoazo dyestuffs can also be obtained by using as diazo components compounds such as the l-amino-(phenoxy-acetanilide) -3- sulfonic acid.

O0 OHr-C ohm-Omen SOIH or the l-amino-(2-napthoXyacetanilide) -3- sulfonic acid or also the 3.5-dichloro-4-amino- B-phenoXy-propionyl-anilide) may be substituted by halogen, alkyl or alkoxy, R stands for hydrogen which may be replaced by alkyl, or stands for one of the numbers one, two and three, one R stands for the residue of a coupling component capable of producing an azodyestufl', the other R3 stands for the residue of a diazotization component capable of'producing an azodyestufi", said dyestufis being various colored powders, easily soluble in water if they contain an acid group, dyeing wool in an acid bath evenly various shades of good fastness to light and fulling-and being suitable for discharge printing on wool and the production of valuable lakes or pigments.

2. As a new product the azo dyestufi having in its free state the probable formula:

being a dark powder easily soluble in water, dyeing wool evenly clear reddish violet shades of good fastness'to light, fulling and perspiration.

3. As new products azo dyestufl'sof the general formula of good fastness to light and fulling andbeing suitable for discharge printing on wool and the production of valuable lakes or pigments.

In testimony whereof we have hereunto set our hands.

WINFRID HENTRICH. RUDOLF KNO'CI-IE. 

